Fabric rinse composition comprising a triazine uv absorber

ABSTRACT

Disclosed is a fabric rinse composition comprising a) 0.1 to 10% by weight of a UV absorber selected from a hydroxyaryl-1, 3, 5-triazine of the formula (I), wherein R 1  is hydrogen; c 1 -c 4 -Alkoxy; or halogen; R 2  is mono-C 1 -C 4  alkylamino; a radical of the formula (I′); X is C 2 -C 4  alkylen; Y 1 , Y 2  independently from each other are C 1 -C 4  alkyl or C 1 -C 4  alkyl which is substituted by halogen, cyano hydroxy or C 1 -C 4  alkoxy; or Y 1  and Y 2  or Y 1  and Y 3  together with the nitrogen atom form a 5- to 7-membered heterocycle; Y 3  is hydrogene; C 1 -C 4  alkyl; C 3 -C 4  alkenyl; or C 1 -C 4  alkyl, C 3 -C 4  alkenyl which is substituted by cyano, hydroxy, C 1 -C 4  alkoxy, phenyl or C 1 -C 4  alkoxycarbonyl; or Y 1 , Y 2  and Y 3  together with the binding nitrogen atom form a pyrrolidine, piperidine or morpholine radical; A is the counter ion; b) 5 to 25% by weight, based on the total weight of the composition of a fabric care ingredient; and c) the remainder being substantially water.

[0001] The present invention relates to a composition for the treatmentof textiles, in particular to a fabric care composition containing a UVabsorber; and to a method of treating textiles with the composition,which method imparts to textile fiber material so treated, in additionto an excellent UV Protecting Eactor (UPF), and other desirableproperties.

[0002] It is known that light radiation of wavelengths 280-400 nmpermits tanning of the epidermis. Also known is that rays of wavelengths280-320 nm (termed UV-B radiation), cause erythemas and skin burningwhich can inhibit skin tanning.

[0003] Radiation of wavelengths 320-400 nm (termed UV-A radiation) isknown to induce skin tanning but can also cause skin damage, especiallyto sensitive skin which is exposed to sunlight for long periods.Examples of such damage include loss of skin elasticity and theappearance of wrinkles, promotion of the onset of erythemal reaction andthe inducement of phototoxic or photoallergic reactions.

[0004] Any effective protection of the skin from the damaging effects ofundue exposure to sunlight clearly needs to include means for absorbingboth UV-A and UV-B components of sunlight before they reach the skinsurface.

[0005] Traditionally, protection of exposed human skin against potentialdamage by the UV components in sunlight has been effected by directlyapplying to the skin a preparation containing a UVA. In areas of theworld, e.g. Australia and America, which enjoy especially sunnyclimates, there has been a great increase in the awareness of thepotential hazards of undue exposure to sunlight, compounded by fears ofthe consequences of alleged damage to the ozone layer. Some of the moredistressing embodiments of skin damage caused by excessive, unprotectedexposure to sunlight are development of melanomas or carcinomas on theskin.

[0006] One aspect of the desire to increase the level of skin protectionagainst sunlight has been the consideration of additional measures, overand above the direct protection of the skin.

[0007] For example, consideration has been given to the provision ofprotection to skin covered by clothing and thus not directly exposed tosunlight.

[0008] Most natural and synthetic textile materials are at leastpartially permeable to UV components of sunlight. Accordingly, the merewearing of clothing does not necessarily provide skin beneath theclothing with adequate protection against damage by UV radiation.Although clothing containing a deeply coloured dye and/or having a tightweave texture may provide a reasonable level of protection to skinbeneath it, such clothing is not practical in hot sunny climates, fromthe standpoint of the personal comfort of the wearer.

[0009] There is a need, therefore, to provide protection against UVradiation for skin which lies underneath clothing, including lightweightsummer clothing, which is undyed or dyed only in pale shades. Dependingon the nature of the dyestuff, even skin beneath clothing dyed in somedark shades may also require protection from UV radiation.

[0010] Such lightweight summer clothing normally has a density of ofless than 200 g/m² and has a sun protection factor rating between 1.5and 20, depending on the type of fiber from which the clothing ismanufactured.

[0011] The UPF rating of a sun protectant (sun cream or clothing) may bedefined as the multiple of the time taken for the average person wearingthe sun protectant to suffer sun burning under average exposure to sun.For example, if an average person would normally suffer sun burn after30 minutes under standard exposure conditions, a sun protectant havingan UPF rating of 5 would extend the period of protection from 30 minutesto 2 hours and 30 minutes. For people living in especially sunnyclimates, where mean sun burn times are minimal, e.g. only 15 minutesfor an average fair-skinned person at the hottest time of the day, UPFratings of about 20 are desired for lightweight clothing.

[0012] The selection of a suitable UVA, for use in a method foreffecting an increase in the UPF value of a textile fiber material(often referred to as a “UV cutting” treatment method), has to take intoaccount the fact that the treated textile fiber material must satisfyperformance criteria in a wide range of areas, such as washfastness,lightfastness and tear resistance, apart from its UPF value.

[0013] For example, the currently known non-reactive UVAs generallyexhibit an inadequate washfastness when applied to cotton. Consequently,their use in UV cutting applications (and also for the purpose ofimproving the lightfastness) is limited.

[0014] The present invention provides, therefore, as a first aspect, astable, concentrated fabric rinse composition comprising

[0015] a) 0.1 to 10, preferably 0.1 to 5% by weight of a UV absorberselected from a hydroxyaryl-1,3,5-triazine of the formula

[0016] wherein

[0017] R₁ is hydrogen; C₁-C₄alkyl; C₁-C₄-Alkoxy; or halogen;

[0018] R₂ is mono-C₁-C₄alkylamino; di-C₁-C₄alkylamino; a radical of theformula

[0019] X is C₂-C₄alkylen;

[0020] Y₁, Y₂ independently from each other are C₁-C₄alkyl or C₁-C₄alkylwhich is substituted by halogen, cyano hydroxy or C₁-C₄alkoxy; or Y₁andY₂ or Y₁ and Y₃ together with the nitrogen atom form a 5- to 7-memberedheterocycle

[0021] Y₃ is hydrogen; C₁-C₄alkyl; C₃-C₄alkenyl; or C₁-C₄alkyl,C₃-C₄alkenyl which is substituted by cyano, hydroxy, C₁-C₄alkoxy, phenylor C₁-C₄alkoxycarbonyl; or

[0022] Y₁, Y₂ and Y₃ together with the binding nitrogen atom form apyrrolidine, piperidine or morpholine radical;

[0023] A is the counter ion;

[0024] b) 5 to 25% by weight, based on the total weight of thecomposition of a fabric care ingredient; and

[0025] c) the remainder being substantially water.

[0026] Preferably in the present composition UV absorbers of formula

[0027] is used, wherein

[0028] R₁ is hydrogen or C₁-C₅alkyl;

[0029] R₂ is mono-C₁-C₅alkylamino; di-C₁-C₅alkylamino; a radical of theformula

[0030] X is C₂-C₄alkylen;

[0031] Y₁, Y₂ and Y₃ independently from each other are C₁-C₅alkyl; and

[0032] A is as defined as in formula (1).

[0033] Preferably, in formula (2)

[0034] R₁ is hydrogen or C₁-C₂alkyl;

[0035] R₂ is di-C₁-C₂alkylamino; N⁺(C₁-C₂alkyl)₃—A⁻;N⁺(C₁-C₂alkyl)₂CH₃—A⁻; and

[0036] A is as defined as in formula (1).

[0037] A is preferably selected from

[0038] or I⁻.

[0039] Most preferably, in formula (2)

[0040] R₂ is —N(CH₃)₃; —N(C₂H₅)₂; —N⁺(CH₃)₃A⁻; or —N⁺(C₂H₅)CH₃A⁻.

[0041] Mostly preferred are compounds of formula (2) wherein

[0042] R₁ is hydrogen or methyl;

[0043] R₂ is —N(CH₃)₃; —N(C₂H₅)₂; —N⁺(CH₃)₃A⁻; or —N⁺(C₂H₅)CH₃A⁻;

[0044] X is —CH₂CH₂—; or —CH₂—CH₂—CH₂—, and

[0045] A is

[0046] or I⁻.

[0047] The UV absorber used in the present composition readily absorbsUV light, especially in the range I=300 to 400 nm, and converts theabsorbed energy, by a chemical intermediate reaction, intonon-interfering, stable compounds or into non-interfering forms ofenergy. The UV absorber should, of course, be compatible with the rinsecycle fabric softener composition. Preferably, the UV absorber used isone which is capable of being absorbed on to the washed textile articleduring a rinse cycle fabric softener treatment.

[0048] Preferred UV absorbers used in the present composition are listedin Table 1: TABLE 1

Compound of formula R₁ R₂ X Counter ion (1a) H N(C₂H₅)₂ —(CH₂)₂— — (1b)CH₃ N⁺(CH₃)₃ —(CH₂)₂— I⁻ (1c) CH₃ N(CH₃)₂ —(CH₂)₂— — (1d) CH₃ N⁺(CH₃)₃—(CH₂)₂— hydrogensulfate/ methosulfate

[0049] TABLE 1

Compound of formula R₁ R₂ X Counter ion (1e) H N⁺(C₂H₅)₂CH₃ —(CH₂)₂— I⁻(1f) H N⁺(C₂H₅)₂CH₃ —(CH₂)₂— hydrogensulfate/ methosulfate (1g) HN⁺(CH₃)₃ —(CH₂)₃— hydrogensulfate/ methosulfate (1h) CH₃ N⁺(CH₃)₃—(CH₂)₃— hydrogensulfate/ methosulfate (1i) CH₃ N⁺(C2H5)CH₃ —(CH₂)₂—hydrogensulfate/ methosulfate

[0050] The counter-ions hydrogensulfate and methosulfate are formeddepending on varying reaction conditions and are present in differentweight ratios.

[0051] The compounds of formula (1) are known and may be prepared in themanner, e.g., described in EP-A-0357545.

[0052] Fabric softeners (component (b)) suitable for use herein areselected from the following classes of compounds:

[0053] (i) Cationic quaternary ammonium salts. The counter ion of suchcationic quaternary ammonium salts may be a halide, such as chloride orbromide, methyl sulphate, or other ions well known in the literature.Preferably the counter ion is methyl sulfate or any alkyl sulfate or anyhalide, methyl sulfate being most preferred for the dryer-added articlesof the invention.

[0054] Examples of cationic quaternary ammonium salts include but arenot limited to:

[0055] 1. Acyclic quaternary ammonium salts having at least two C₈ toC₃₀, preferably C₁₂ to C₂₂ alkyl or alkenyl chains, such as:ditallowdimethyl ammonium methylsulfate, di(hydrogenated tallow)dimethylammonium methylsulfate, distearyldimethyl ammonium methylsulfate orchloride, dicocodimethyl ammonium methylsulfate and the like. It isespecially preferred if the fabric softening compound is a waterinsoluble quaternary ammonium material which comprises a compound havingtwo C₁₂ to C₁₈ alkyl or alkenyl groups connected to the molecule via atleast one ester link. It is more preferred if the quaternary ammoniummaterial has two ester links present. An especially preferredester-linked quaternary ammonium material for use in the invention canbe represented by the formula:

[0056] wherein each R₃ group is independently selected from C₁ to C₄alkyl, hydroxyalkyl or C₂ to C₄ alkenyl groups; T is either

[0057] and wherein each R₄ group is independently selected from C₈ toC₂₈ alkyl or alkenyl groups; and e is an integer from 0 to 5.

[0058] A second preferred type of quaternary ammonium material can berepresented by the formula:

[0059] wherein R₃, e and R₄ are as defined above.

[0060] 2. Cyclic quaternary ammonium salts of the imidazolinium typesuch as di(hydrogenated tallow)dimethyl imidazolinium methylsulfate,1-ethylene-bis(2-tallow-1-methyl) imidazolinium methylsulfate and thelike;

[0061] 3. Diamido quaternary ammonium salts such as:methyl-bis(hydrogenated tallow amidoethyl)-2-hydroxethyl ammonium methylsulfate, methyl bi(tallowamidoethyl)-2-hydroxypropyl ammoniummethylsulfate and the like;

[0062] 4. Biodegradable quaternary ammonium salts such asN,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium methyl sulfate andN,N-di(tallowoyl-oxy-propyl)-N,N-dimethyl ammonium methyl sulfate.Biodegradable quaternary ammonium salts are described, for example, inU.S. Pat. Nos. 4,137,180, 4,767,547 and 4,789,491 incorporated byreference herein.

[0063] Preferred biodegradable quaternary ammonium salts include thebiodegradable cationic diester compounds as described in U.S. Pat. No.4,137,180, herein incorporated by reference.

[0064] (ii) Tertiary fatty amines having at least one and preferably twoC₈-C₃₀, preferably C₁₂-C₂₂ alkyl chains. Examples include hardenedtallow-di-methylamine and cyclic amines such as 1-(hydrogenatedtallow)amidoethyl-2-(hydrogenated tallow) imidazoline. Cyclic amineswhich may be employed for the compositions herein are described in U.S.Pat. No. 4,806,255 incorporated by reference herein.

[0065] (iii) Carboxylic acids having 8 to 30 carbons atoms and onecarboxylic group per molecule. The alkyl portion has 8 to 30, preferably12 to 22 carbon atoms. The alkyl portion may be linear or branched,saturated or unsaturated, with linear saturated alkyl preferred. Stearicacid is a preferred fatty acid for use in the composition herein.Examples of these carboxylic acids are commercial grades of stearic acidand palmitic acid, and mixtures thereof which may contain small amountsof other acids.

[0066] (iv) Esters of polyhydric alcohols such as sorbitan esters orglycerol stearate. Sorbitan esters are the condensation products ofsorbitol or iso-sorbitol with fatty acids such as stearic acid.Preferred sorbitan esters are monoalkyl. A common example of sorbitanester is SPAN 60 (ICI) which is a mixture of sorbitan and isosorbidestearates.

[0067] (v) Fatty alcohols, ethoxylated fatty alcohols, alkylphenols,ethoxylated alkylphenols, ethoxylated fatty amines, ethoxylatedmonoglycerides and ethoxylated diglycerides.

[0068] (vi) Mineral oils, and polyols such as polyethylene glycol.

[0069] These softeners are more definitively described in U.S. Pat. No.4,134,838 the disclosure of which is incorporated by reference herein.Preferred fabric softeners for use herein are acyclic quaternaryammonium salts. Di(hydrogenated)tallowdimethyl ammonium methyl-sulfateis most widely used for dryer articles of this invention. Mixtures ofthe above mentioned fabric softeners may also be used.

[0070] In addition, the composition according to the present inventionmay also contain a minor proportion of one or more adjuvants. Examplesof adjuvants include emulsifiers, perfumes, colouring dyes, opacifiers,fluorescent whitening agents, bactericides, nonionic surfactants,anti-gelling agents such as nitrites or nitrates of alkali metals,especially sodium nitrate, and corrosion inhibitors such as sodiumsilicate.

[0071] The amount of each of these optional adjuvants preferably rangesfrom 0.05 to 5% by weight of the composition.

[0072] A particularly preferred optional adjuvant is a cationic,amphoteric or anionic fluorescent whitening agent as disclosed inEP-A-0,659,877, from page 9 to page 15, line 56.

[0073] The present invention also provides, as a third aspect, a methodfor the treatment of a textile article, in particular to improve itsUPF, comprising applying, to a previously washed article, a fabric rinsecomposition comprising:

[0074] a) 0.1 to 10, preferably 0.1 to 5% by weight of a UV absorber offormula (1), based on the total weight of the composition;

[0075] b) 5 to 25%, especially from 10 to 20% by weight, based on thetotal weight of the composition, of a fabric care ingredient; and

[0076] c) the remainder being substantially water.

[0077] Preferably, the fabric care ingredient is a fabric softener, astain release or stain repellent ingredient or a water-proofing agent.

[0078] A preferred method for the treatment of a textile article, inparticular to improve its UPF comprises applying, to the previouslywashed article, a rinse cycle fabric softener composition comprising:

[0079] a) 0.05 to 5, preferably 0.1 to 1.5% by weight of a UV absorberof formula (1), based on the total weight of the composition;

[0080] b) 5 to 25, preferably 10 to 20% by weight of a cationic fabricsoftening agent, based on the total weight of the composition; and

[0081] c) the remainder being substantially water.

[0082] The textile article treated according to the method of thepresent invention may be composed of any of a wide range of types offiber such as wool, polyamide, cotton, polyester, polyacrylic, silk orany mixture thereof.

[0083] The method and composition of the present invention, in additionto providing protection to the skin, also increase the useful life of atextile article treated according to the present invention, for exampleby preserving its tear strength and/or its lightfastness.

[0084] The following Examples further illustrate the present invention.

EXAMPLE 1

[0085] 5 g of bleached cotton fabric are washed/rinsed in a linitestapplying the following conditions:

[0086] Main Wash: Detergent dosage: 4 g/l ECE 77 (phosphate containingstandard detergent which is free of fluorescent whitening and bleachinggents) Liquor ratio: 1:20 Duration: 15 minutes Temperature: 25° C.

[0087] Rinsing is carried out with tap water for 30 seconds and the spindried.

[0088] Rinse Bath: Softener dosage: 1.66 g/l concentrated Esterquat or 5g/l diluted DSDMAC Liquor ration: 1:40 Duration: 15 minutes Temperature:25° C.

[0089] The fabric is spin dried at 60° C.; 1 and 3 wash cycles TABLE 2Softener formulation: Esterquat DSDMAC formulation formulationDi-(palmcarboxyethyl)-hydroxyethyl-   15% — methylammonium-methosulfateactive (Rewoquat WE 38 DPG) matter Distearyl-dimethylammoniumchloride —  5% (Arquad 2 HT-75) active matter C₁₂-C₁₃ fatty alcohol ethoxylatewith —  0.5% an average of 6 EO units (Dobanol 23-6.5) MgCl₂  0.1% —UV-Absorber of formulas (1a), (1f) and  2.4%  0.8% (1 g) water ad ad 100%  100%

[0090] The UPF of the dried softener treated goods are determined.

[0091] The UPF is determined by measurement of the UV light transmittedthrough the textile, using a double grating spectrophotometer fittedwith an Ulbricht bowl. Calculation of UPF is conducted as described byB. L. Diffey and J. Robson in J. Soc. Cosm. Chem. 40 (1989), pp.130-131.

[0092] The results are shown in Table 3: TABLE 3 softener formulationwithout UV Compound of formula absorber (1f) (1g) (1a) DSDMACformulation 1^(st) wash/rinse 4 24 19 13 3^(rd) wash/rinse 4 41 40 19Esterquat formulation 1^(st) wash/rinse 4 — 14 9 3^(rd) wash/rinse 4 —35 16

[0093] The results in Table 1 and 2 clearly demonstrate the improvementof the UPF values of the cotton substrates treated with rinsecompositions according to the present invention.

1. fabric rinse composition comprising a) 0.1 to 10% by weight of a UVabsorber selected from a hydroxyaryl-1,3,5-triazine of the formula

wherein R₁ is hydrogen; C₁-C₄alkyl; C₁-C₄-Alkoxy; or halogen; R₂ ismono-C₁-C₄alkylamino; di-C₁-C₄alkylamino; a radical of the formula

X is C₂-C₄alkylen; Y₁, Y₂ independently from each other are C₁-C₄alkylor C₁-C₄alkyl which is substituted by halogen, cyano hydroxy orC₁-C₄alkoxy; or Y₁ and Y₂ or Y₁ and Y₃ together with the nitrogen atomforn a 5- to 7-membered heterocycle; Y₃ is hydrogen; C₁-C₄alkyl;C₃-C₄alkenyl; or C₁-C₄alkyl, C₃-C₄alkenyl which is substituted by cyano,hydroxy, C₁-C₄alkoxy, phenyl or C₁-C₄alkoxycarbonyl; or Y₁, Y₂ and Y₃together with the binding nitrogen atom form a pyrrolidine, piperidineor morpholine radical; A is the counter ion; b) 5 to 25% by weight,based on the total weight of the composition of a fabric careingredient; and c) the remainder being substantially water:
 2. Acomposition according to claim 1 of formula

wherein R₁ is hydrogen or C₁-C₅alkyl; R₂ is mono-C₁-C₅alkylamino;di-C₁-C₅alkylamino; a radical of the formula

X is C₂-C₄alkylen; Y₁, Y₂ and Y₃ independently from each other areC₁-C₅alkyl; and A is as defined as in claim
 1. 3. A compositionaccording to claim 1 or 2 wherein R₁ is hydrogen or C₁-C₂alkyl.
 4. Acomposition according to any one of claims 1 to 3 wherein R₂ isdi-C₁-C₂alkylamino; N⁺(C₁-C₂alkyl)₃—A⁻; N⁺(C₁-C₂alkyl)₂CH₃—A⁻; and A isas defined as in claim
 1. 5. A composition according to claim 4 whereinR₂ is —N(CH₃)₃; —N(C₂H₅)₂; —N⁺(CH₃)₃A⁻; or —N⁺(C₂H₅)CH₃A⁻.
 6. Acomposition according to any one of claims 2 to 5 wherein R₁ is hydrogenor methyl; R₂ is —N(CH₃)₃; —N(C₂H₅)₂; —N⁺(CH₃)₃A⁻; or —N⁺(C₂H₅)CH₃A⁻; Xis —CH₂CH₂—; or —CH₂—CH₂—CH₂—; and A is

or I⁻.
 7. A composition according to any of the preceding claims whereinA is selected from

or I⁻.
 8. A composition according to any of the preceding claims inwhich the fabric care ingredient is selected from cationic quaternaryammonium salts, tertiary fatty amines having at least one C₈-C₃₀ alkylchain, carboxylic acids having 8 to 30 carbons atoms and one carboxylicgroup per molecule, esters of polyhydric alcohols, fatty alcohols,ethoxylated fatty alcohols, alkyphenols, ethoxylated alkyphenols,ethoxylated fatty amines, ethoxylated monoglycerides and ethoxylateddiglycerides.
 9. A composition according to claim 8, wherein cationicquaternary ammonium salt fabric softener is selected from acyclicquaternary ammonium salts having at least two C₈ to C₃₀ alkyl or alkenylchains ,cyclic quaternary ammonium salts, diamido quaternary ammoniumsalts and biodegradable quaternary ammonium salts.
 10. A compositionaccording to claim 9, wherein acyclic quaternary ammonium saltscorrespond to formula

wherein each R₃ group is independently selected from C₁ to C₄ alkyl,hydroxyalkyl or C₂ to C₄ alkenyl groups; T is either

and wherein each R₄ group is independently selected from C₈ to C₂₈ alkylor alkenyl groups; and e is an integer from 0 to
 5. 11. A compositionaccording to claim 9, wherein acyclic quaternary ammonium saltscorrespond to formula

wherein each R₃ group is independently selected from C₁ to C₄ alkyl,hydroxyalkyl or C₂ to C₄ alkenyl groups; and each R₄ group isindependently selected from C₈ to C₂₈ alkyl or alkenyl groups; and e isan integer from 0 to
 5. 12. A composition according to claim 10, whereinthe acyclic quaternary ammonium salt isdi-(palmcarboxyethyl)-hydroxyethyl-methylammonium-methosulfate.
 13. Acomposition according to claim 10, wherein the acyclic quaternaryammonium salt is selected from ditallowdimethyl ammonium methylsulfate,di(hydrogenated tallow)dimethyl ammonium methylsulfate,distearyldimethyl ammonium methylsulfate or chloride and dicocodimethylammonium methylsulfate.
 14. A composition according to claim 8 or 9, inwhich the biodegradable quaternary ammonium salts are selected fromN,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium methyl sulfate andN,N-di(tallowoyl-oxy-propyl)-N,N-dimethyl ammonium methyl sulfate.
 15. Acomposition according to any of the preceding claims which also containsan adjuvant selected from an emulsifier, perfume, colouring dye,opacifier, fluorescent whitening agent, bactericide, nonionicsurfactant, anti-gelling agent and corrosion inhibitor.
 16. A method forthe treatment of a textile article, comprising applying, to a previouslywashed article, a fabric rinse composition comprising a) 0.1 to 10% byweight of a UV absorber of formula (1), based on the total weight of thecomposition; b) 5 to 25% by weight, based on the total weight of thecomposition, of a fabric care ingredient; and c) the remainder beingsubstantially water.
 17. A method according to claim 18 in which thetextile article treated is composed of wool, polyamide, cotton,polyester, polyacrylic, silk or any mixture thereof.
 18. A methodaccording to claim 18 or 19 in which the UPF value of the treatedtextile article is improved.
 19. A method according to claim 18 or 19 inwhich the tear strength and/or the lightfastness of the treated textilearticle is improved.